Simulation of ab initio optical absorption spectrum of \beta-carotene with fully resolved S_{0} and S_{2} vibrational normal modes

Abstract

Electronic absorption spectrum of beta-carotene (b-Car) is studied using quantum chemistry and quantum dynamics simulations. Vibrational normal modes were computed in optimized geometries of the electronic ground state S0 and the optically bright excited S2 state using the time-dependent density functional theory. By expressing the S2 state normal modes in terms of the ground state modes, we find that no one-to-one correspondence between the ground and excited state vibrational modes exists. Using the ab initio results, we simulated b-Car absorption spectrum with all 282 vibrational modes in a model solvent at 300K using the time-dependent Dirac-Frenkel variational principle (TDVP) and are able to qualitatively reproduce the full absorption lineshape. By comparing the 282-mode model with the prominent 2-mode model, widely used to interpret carotenoid experiments, we find that the full 282-mode model better describe the high frequency progression of carotenoid absorption spectra, hence, vibrational modes become highly mixed during the S0 -> S2 optical excitation. The obtained results suggest that electronic energy dissipation is mediated by numerous vibrational modes.